CN105958027A - Manganese-based composite positive electrode material and preparation method therefor - Google Patents

Manganese-based composite positive electrode material and preparation method therefor Download PDF

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CN105958027A
CN105958027A CN201610459045.4A CN201610459045A CN105958027A CN 105958027 A CN105958027 A CN 105958027A CN 201610459045 A CN201610459045 A CN 201610459045A CN 105958027 A CN105958027 A CN 105958027A
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lithium
manganese
lanthanum
chromium
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CN105958027B (en
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高羽
程杰
朱寅中
高申元
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Guangxi Pingguo Runmin Poverty Alleviation Development Co., Ltd
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Guizhou Yuping Marvell Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to the manufacturing technical field of a battery material, and particularly to a manganese-based composite positive electrode material and a preparation method therefor. Through the matching of a manganese source, a lithium source, a chromium source, a lanthanum source, a binder, a solvent and spinel lithium manganate particles, the spinel lithium manganate particles can be taken as the core; a high-valance lithium-rich phase can be formed in the middle layer and a low-valence Li<2>MnO<2> phase can be formed in the outer layer; consequently, the spinel lithium manganate energy storage part is formed in the interior; the high-valance lithium-rich phase energy storage part is formed in the middle; the Li<2>MnO<2> phase energy storage part is formed in the outer layer; the specific capacity of the positive electrode material is effectively improved; the outer layer of the spinel lithium manganate particles is coated with the low-valance-state material, so that the dissolution of the spinel lithium manganate and the attenuation of the high-valence lithium-rich phase in the middle layer are effectively restrained; and the outer layer is coated with the phase with much lithium, so that the rate of decay of the positive electrode is effectively lowered and the specific capacity of the positive electrode material is improved.

Description

A kind of manganio composite positive pole and preparation method thereof
Technical field
The present invention relates to battery material manufacture technology field, especially a kind of manganio anode composite material Material and preparation method thereof.The invention belongs to Electrochemical Engineering and commercial plant field, and it can As electrode active material, it is applied to the lithium-ion battery system of aqueous solution and organic electrolyte Or in the lithium battery system of organic electrolyte.
Background technology
It is since human society marches toward industrialization, huge to the demand of the fossil energy such as coal and oil, Along with the non-renewable energy resources such as coal and oil huge consumption and resource lacks day by day.Carbon dioxide Discharge aggravation greenhouse effect and the most serious air, ecological environment pollution to us The rely earth home of life constitutes more severe threat.Greatly develop wind energy, solar energy It is to realize the important channel of China's energy sustainable development etc. regenerative resource.Development of renewable energy Electricity has time difference property and unstability, limits its large-scale grid connection and utilizes.Electric power storage is that solution can One of effective ways of instability problem of the renewable sources of energy, can realize regenerative resource extensive Application.
Along with to electric power storage solve renewable sources of energy instability problem research and explore during, right Quick development and conceptual phase have been stepped in research in battery；In the nineties in last century, Lithium rechargeable battery obtains industrialization in Japan, because it has high voltage, high power capacity, nothing note Recall the performances such as benefit, receive the favor of people, especially at portable type electronic product, communication letter The aspects such as breath application.
Lithium ion battery is owing to himself having energy density and energy transformation ratio height, rated voltage Higher advantage so that it has obtained developing faster；And in lithium ion battery, its positive pole Material is the material of key, and the performance of positive electrode affects lithium ion to a great extent The performance of battery, the index such as energy force density, life-span and safety of which determining lithium battery, its Cost shared in lithium ion battery reaches 30-40%.
Research for anode material for lithium-ion batteries mainly has lithium cobalt oxide, lithium nickel oxygen and lithium in early days Several systems such as manganese oxygen；Lithium oxygen plus plate material is owing to its preparation technology is relatively simple, performance is steady Determine, specific capacity is high and cyclicity is good, is main in current commercial lithium-ion batteries just employing Pole material, but the price of cobalt is high, poor stability, when the most large-scale, motive-power battery is applied Poor stability, is mainly used in miniaturized electronics, it is difficult in the bigger application of the energy storage capacities such as electric motor car Field is promoted；Lithium nickel oxygen (LiNiO2) has a layer structure similar to lithium cobalt oxide, specific energy is high, Cycle performance is preferable, moderate, but the condition preparing lithium nickel oxygen is the harshest, applies the widest； Lithium manganese-oxygen material have abundant raw material, with low cost, without advantages such as environmental hazards, but it is higher At a temperature of dissolve cause capacitance loss, cycle life is the highest, and specific capacity is relatively low, although existing skill In art, researcher is had to be doped for this series products with elements such as Ni, Co, Cr, improve Li/Mn Ratio, reaches to improve the purpose of drawbacks described above, but still makes the specific volume of the lithium manganese-oxygen material of preparation Amount is about 120-130mAh/g so that the poor-performing of lithium ion battery.And, Ni, Co The cost being doped material Deng element increases more.
To this end, prior art occurs in that again other technological means, such as phosphate LiMPO4 (M=Fe, Co, Ni, Mn, V etc.), Li3V2(PO4)3, silicate Li2MSiO4(M=Fe, And titanate Li Mn)2MTiO4(M=Ni, Fe, Mn), but above-mentioned material of the prior art Specific capacity the most relatively low, and then cause the specific energy of battery of preparation the most relatively low, even have Material also can be too high because of current potential, cause electrolyte decomposition so that battery shorten Phenomenon occur.
The reason causing above-mentioned phenomenon to occur is: the either LiMO of stratiform2(include LiCoO2、 LiNi1/3Co1/3Mn1/3O2Ex hoc genus anne thing), or the LiMn of spinel-type2O4, or olivine The LiMPO of type4Deng, each of which molecule comprises only the transition element atom of variable 1 valency, The lithium ion that can remove when charging is made to be up to one, the LiMO that molecular weight is minimum2, The specific capacity of its theory is about 274mAh/g so that it is guaranteeing the stability of crystal structure Time, it is possible to the lithium ion of removing is only 0.5-0.65 so that the specific capacity of its reality is About 140mAh/g, causes the specific energy with its battery prepared for cell positive material relatively low； Further, stratiform and the solid-solution material of spinelle or olivine-type material etc., at it, there is rich lithium When appraising at the current rate of the trivalent of manganese, tetravalence and M, it is possible to make its specific capacity higher, but, this After class material is prepared as battery, owing to the voltage of rich lithium manganese material is higher, it is easily caused electrolyte Decomposing, special capacity fade is very fast so that the service life of the battery of preparation is poor.
In consideration of it, this researcher is by studying manganio combination electrode material and explore, carry For specific capacity height, low cost, activity is high, can be prevented effectively from electrolyte decomposition, reduces specific volume The manganio composite positive pole of the amount rate of decay, receives offer for anode material for lithium ion battery A kind of new approaches.
Summary of the invention
In order to solve above-mentioned technical problem present in prior art, the present invention provides a kind of manganio Composite positive pole and preparation method thereof.
Emerge from particular by techniques below scheme:
A kind of manganio composite positive pole, its be manganese source, lithium source, chromium source, lanthanum source, binding agent, Solvent composition covering be coated on outside spinel lithium manganate granule, wherein manganese source, lithium source, chromium source, The proportioning in lanthanum source is so that in covering, the atomic ratio of lithium, lanthanum, chromium and manganese is 1.91-1.55: 0.03-0.15∶0.03-0.15∶0.97-0.85；Wherein the consumption of binding agent is manganese source, lithium Source, chromium source, the mass percent of the total consumption in lanthanum source are calculated as 1-10%, the consumption of solvent be manganese source, Lithium source, chromium source, the quality of the total consumption in lanthanum source are calculated as 5-50 times.Make the manganio obtained compound just Outer layer manganese in the material of pole is in relatively lower valency, and containing multiple available lithium ions, carries The high specific capacity of positive electrode.Processed by chromium source, lanthanum source doping so that form internal point Spar LiMn2O4 energy storage, the rich lithium phase energy storage of intermediate formation high price, outer layer form Li2MnO2Phase energy storage, Effectively raise the specific capacity of positive electrode, and by spinel lithium manganate granule outer layer bag Cover the material of lower valency, effectively inhibit spinel lithium manganate to dissolve and intermediate layer high price is rich The decay of lithium phase, and in the external sheath phase containing more lithium so that it effectively improves positive pole material Material the rate of decay and improve its specific capacity.
Above-mentioned employing is coated on outside spinel lithium manganate, and it is in order to by being coated on spinel manganese Acid lithium granule outside, reach to alleviate the stress of change in volume, prevent intermediate layer high price richness lithium phase, The Li of outer layer2MnO2In discharge and recharge, change in volume is big, and fast charging and discharging is easily caused granule and breaks Split so that the defect of specific capacity rapid decay, reduce height ratio capacity material generation side reaction and decline The probability subtracted.
The preparation method of above-mentioned manganio composite positive pole is to put in solvent by binding agent, molten Solution becomes solution, then is added thereto to spinel lithium manganate granule, stirs into suspension, and adds Manganese source, lithium source, chromium source, lanthanum source, in adition process, control temperature, at 0-120 DEG C, is treated After having added, adjust temperature and be 60-200 DEG C, solvent is steamed completely, is passed through protectiveness gas Body is warmed up to 600-1200 DEG C, isothermal reaction 0.5-48h, cools down, is ground into 6-15 micron, Obtain manganio composite positive pole.By binding agent, raw material is bonded in internal layer spinel lithium manganate Particle surface, after the most first using solvent that binding agent is dissolved into solution, adds spinelle Lithium manganate particle, stirs into suspension, adds manganese source, lithium source, chromium source, lanthanum source, then adjusts Whole temperature processes, and not only so that it can be uniformly coated with, additionally provides reducing agent so that Along with the change of temperature, binding agent therein is decomposed, and decomposites reducibility gas and carbon, And by the manganese of high temperature reduction high-valence state, chromium so that the outer layer at positive electrode forms lower valency The Li of doping2MnO2Phase, the carbon that binding agent itself decomposes simultaneously, outside can being uniformly coated on Layer, improves the electron conduction of composite positive pole；Meanwhile, binding agent in catabolic process, Portion gas is escaped, and forms tiny hole on the surface of positive electrode, increases the ratio of positive electrode Surface area so that the active substance within positive electrode can occur sufficiently with electrolyte solution Contact.
In above-mentioned temperature-rise period, its programming rate is 0.1-200 DEG C/min.
Above-mentioned programming rate is when 0.1-20 DEG C/min, and it uses electrical heating to heat up, and is heating up When speed is 20 DEG C/more than min, it uses microwave heating hyperthermic treatment.
By using above-mentioned heating mode to process so that manganio composite positive pole is at high temperature Primary granule size during reason is easily controllable, it is to avoid high-temperature process causes spinelle mangaic acid Lithium granule kernel is reacted conversion completely, additionally it is possible to promote quickly to generate intermediate layer and outer layer, The secondary granule that tap density height, intermediate layer and the outer layer of the positive electrode obtained are formed is big Little uniformly, the loading density of positive electrode is higher.
Above-mentioned manganese source be manganese monoxide, manganese sesquioxide managnic oxide, mangano-manganic oxide, manganese dioxide, Hydroxyl oxidize manganese, manganese nitrate, manganese oxalate, manganese carbonate, formic acid manganese, manganese acetate, high manganese lithium, LiMn2O4, spinel lithium manganate at least one.
Above-mentioned lithium source is lithium nitrate, lithium oxalate, lithium carbonate, lithium formate, Quilonorm (SKB), hydrogen-oxygen At least one of change lithium.
Above-mentioned chromium source is chromium oxide, chromic nitrate, chromium+oxalic acid, chromium carbonate, chromic formate, acetic acid At least one of chromium.
Above-mentioned lanthanum source is lanthana, Lanthanum (III) nitrate, lanthanum oxalate, lanthanum carbonate, formic acid lanthanum, acetic acid At least one of lanthanum.
Above-mentioned binding agent be polyacrylonitrile, phenolic resin, epoxy resin, polyvinyl resin, Furfural resin, polyacrylic resin, polyurethane resin, polyvinyl alcohol at least one.
Above-mentioned solvent be water, ethanol, propanol, ethylene glycol, glycerol, benzene, toluene, third Ketone, butanone, butanone, chloromethanes, benzoyl, formic acid, DMF, N- At least one of methyl pyrrolidone.
Above-mentioned spinel lithium manganate granular size is 0.3-10 micron.
The size of the manganio composite positive pole granule of above-mentioned acquisition is 6-15 micron.
Above-mentioned protective gas be air, oxygen, nitrogen, argon, helium, carbon dioxide, At least one in hydrogen；Choosing and being passed through by this protective gas so that the oxidation of manganese The valence state of thing is at Utopian valence state, it is to avoid manganio composite positive pole outer layer manganese Oxide exists with the mixed valence of trivalent or trivalent and tetravalence more than 520 DEG C, it is ensured that just The outer layer of pole material forms Li2MnO2Phase, improves the performance of positive electrode, guarantees in centre simultaneously Layer forms the rich lithium phase of high price.
In order to make the structure of manganio composite positive pole the most stable, improve this positive pole The performance of the battery that material is prepared as anode material of lithium battery, such as specific capacity, service life etc.； It is in preparation process, after binding agent is dissolved into solution, is adding spinel lithium manganate Before granule, also include adding aluminium salt, zinc salt and/or the step of magnesium salt.Wherein addition is divided Do not account for the 0-5% of lithium source quality.Amount at above-mentioned addition aluminium salt, zinc salt and/or magnesium salt can not mistake Many, otherwise will affect the specific capacity of composite positive pole.
Above-mentioned be warming up to 600-1200 DEG C at process time, can transfer at protective gas existence condition It is placed in hermetic container and carries out heat-agglomerating reaction；Also can put into saggar and be placed on gas shield The equipment such as kiln in, wherein protective gas line flow velocity in the reaction chamber is not less than 5cm/min。
The input amount of above-mentioned spinel lithium manganate granule, accounts for solvent by quality ratio 0.01-0.019 times.
Compared with prior art, the technique effect of the present invention is embodied in:
By manganese source, lithium source, chromium source, lanthanum source, binding agent, solvent, spinel lithium manganate The proportioning of grain, enabling form high price with spinel lithium manganate granule as core, in intermediate layer rich Lithium phase, forms Li at a low price at outer layer2MnO2Phase so that the internal spinel lithium manganate energy storage of formation, The rich lithium phase energy storage of intermediate formation high price, outer layer form Li2MnO2Phase energy storage, just effectively raises The specific capacity of pole material, and by the material at spinel lithium manganate granule external sheath lower valency Material, effectively inhibits spinel lithium manganate to dissolve and the decay of the rich lithium phase of intermediate layer high price, And at external sheath phase containing more lithium so that it effectively improves decay speed of positive electrode Spend and improve its specific capacity.
The preparation method of the manganio composite positive pole of the invention is simple to operate, flow process is short, Energy consumption is low, and makes the manganese of manganio composite positive pole outer layer be in relatively lower valency, and contains More than one available lithium ion, effectively raises the specific capacity of positive electrode, and adopts With spinel lithium manganate as core, define in conjunction with the treatment temperature in preparation technology is isoparametric, Avoiding high-temperature process causes spinel lithium manganate granule kernel to be reacted conversion completely, additionally it is possible to Promote quickly to generate intermediate layer and outer layer so that the tap density of the positive electrode of acquisition is high, The secondary granule size that intermediate layer and outer layer are formed is uniform, and the loading density of positive electrode is higher； Alleviate the stress of change in volume, prevent the high price richness lithium phase in intermediate layer, the Li of outer layer2MnO2Xiang In discharge and recharge, change in volume is big, and fast charging and discharging is easily caused breakage of particles so that specific capacity is fast The defect of speed decay, reduces height ratio capacity material generation side reaction and the probability of decay.Additionally, Because the manganio composite positive pole outer layer of the invention is containing more than one available lithium ion, Extra more lithium can be provided, the most inefficient height ratio capacity negative material can be used to form The battery system of high-energy-density.
The preparation technology of the invention is simple, low cost, pollution are few, and it can be applied to In the battery system of organic electrolyte or aqueous solution, its activity is higher, and specific capacity is higher.
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme is further limited Fixed, but claimed scope is not only limited to description.
Embodiment 1
Under room temperature, 1.7g phenolic resin is dissolved into solution by the ethanol using 500g concentration to be 95%； The spinel lithium manganate that 5g granular size concentrates on 0.3-10 micron again adds, and stirring is formed outstanding Supernatant liquid, then by manganese acetate, Lithium hydrate, chromic nitrate, Lanthanum (III) nitrate add, control lithium, lanthanum, The atomic ratio of chromium and manganese is 1.91: 0.03: 0.03: 0.97, feed postition be by manganese acetate, After chromic nitrate, Lanthanum (III) nitrate are pre-mixed uniformly, add stirring 30min, Lithium hydrate is used After 350g water dissolution, adding, constant temperature stirs into suspension；
Above-mentioned suspension is heated to 80 DEG C of process so that deposit is uniformly glued by phenolic resin Conjunction is coated on spinel lithium manganate particle surface, and the time of process is until solvent evaporation completely, obtains To presoma；
Above-mentioned presoma is placed in microwave kiln, with nitrogen for protective gas heating at Reason, nitrogen line flow velocity in microwave kiln is 5cm/min, and uses microwave hyperthermic treatment, Programming rate is 50 DEG C/min, is heated to 1200 DEG C, isothermal reaction 0.5h, and protects at nitrogen Under be cooled to room temperature after, be ground into 6-15 micron, it is thus achieved that manganio composite positive pole.
Above-mentioned manganio composite positive pole is mixed with conductive agent white carbon black, adhesive PVDF, ratio For manganio composite positive pole: white carbon black: PTFE=80: 15: 7, grind with N-Methyl pyrrolidone Size mixing and be coated on 20 microns of thick aluminium foils, being prepared as test electrode.Above-mentioned electrode is cut out It is cut into the circle sheet of diameter 14mm, after suppressing with 0.5MPa pressure, just can be used as lithium ion battery Pole is tested.Using this electrode as positive pole, lithium sheet as negative pole, PC/DME/LiPF6As 2032 type button cells made by electrolyte, constant current 10mA/g charge and discharge electrical measurement between 2.5-4.2V Examination, specific discharge capacity is more than 200mAh/g.
Embodiment 2
Under room temperature, 0.85g phenolic resin is dissolved into molten by the ethanol using 300g concentration to be 95% Liquid；The spinel lithium manganate that 5g granular size concentrates on 0.3-10 micron again adds, and stirs shape Become suspension, then manganese acetate, Lithium hydrate, chromic nitrate, Lanthanum (III) nitrate are added, control lithium, The atomic ratio of lanthanum, chromium and manganese is 1.91: 0.03: 0.03: 0.97, and feed postition is by acetic acid After manganese, chromic nitrate, Lanthanum (III) nitrate are pre-mixed uniformly, add stirring 30min, by hydroxide Lithium, with after 125g water dissolution, adds, and constant temperature stirs into suspension；
Above-mentioned suspension is heated to 60 DEG C of process so that deposit is uniformly glued by phenolic resin Conjunction is coated on spinel lithium manganate particle surface, and the time of process is until solvent evaporation completely, obtains To presoma；
Above-mentioned presoma is placed in muffle furnace, with nitrogen for protective gas heat treated, Nitrogen line flow velocity in muffle furnace is 5cm/min, and hyperthermic treatment, and programming rate is 0.1 DEG C / min, is heated to 600 DEG C, isothermal reaction 48h, and after being cooled to room temperature under nitrogen protection, It is ground into 6-15 micron, it is thus achieved that manganio composite positive pole.
Above-mentioned manganio composite positive pole is mixed with conductive agent white carbon black, adhesive PVDF, ratio For manganio composite positive pole: white carbon black: PTFE=80: 15: 7, grind with N-Methyl pyrrolidone Size mixing and be coated on 20 microns of thick aluminium foils, being prepared as test electrode.Above-mentioned electrode is cut out It is cut into the circle sheet of diameter 14mm, after suppressing with 0.5MPa pressure, just can be used as lithium ion battery Pole is tested.Using this electrode as positive pole, lithium sheet as negative pole, PC/DME/LiPF6As 2032 type button cells made by electrolyte, constant current 10mA/g charge and discharge electrical measurement between 2.5-4.2V Examination, specific discharge capacity is more than 200mAh/g.
Embodiment 3
Under room temperature, 0.85g phenolic resin is dissolved into molten by the ethanol using 500g concentration to be 95% Liquid；The spinel lithium manganate that 5g granular size concentrates on 0.3-10 micron again adds, and stirs shape Become suspension, then manganese acetate, Lithium hydrate, chromic nitrate, Lanthanum (III) nitrate are added, control lithium, The atomic ratio of lanthanum, chromium and manganese is 1.55: 0.15: 0.15: 0.85, and feed postition is by acetic acid After manganese, chromic nitrate, Lanthanum (III) nitrate are pre-mixed uniformly, add stirring 30min, by hydroxide Lithium, with after 250g water dissolution, adds, and constant temperature stirs into suspension；
Above-mentioned suspension is heated to 80 DEG C of process so that deposit is uniformly glued by phenolic resin Conjunction is coated on spinel lithium manganate particle surface, and the time of process is until solvent evaporation completely, obtains To presoma；
Above-mentioned presoma is placed in microwave oven, with nitrogen for protective gas heat treated, Nitrogen line flow velocity in microwave oven is not less than 5cm/min, and uses microwave hyperthermic treatment, rises Temperature speed is 60 DEG C/min, is heated to 850 DEG C, isothermal reaction 0.5h, and under nitrogen protection After being cooled to room temperature, it is ground into 6-15 micron, it is thus achieved that manganio composite positive pole.
Above-mentioned manganio composite positive pole is mixed with conductive agent white carbon black, adhesive PVDF, ratio For manganio composite positive pole: white carbon black: PTFE=80: 15: 7, grind with N-Methyl pyrrolidone Size mixing and be coated on 20 microns of thick aluminium foils, being prepared as test electrode.Above-mentioned electrode is cut out It is cut into the circle sheet of diameter 14mm, after suppressing with 0.5MPa pressure, just can be used as lithium ion battery Pole is tested.Using this electrode as positive pole, lithium sheet as negative pole, PC/DME/LiPF6As 2032 type button cells made by electrolyte, constant current 10mA/g charge and discharge electrical measurement between 2.5-4.2V Examination, specific discharge capacity is more than 190mAh/g.
Embodiment 4
Under room temperature, 0.85g phenolic resin is dissolved into molten by the ethanol using 275g concentration to be 95% Liquid；The spinel lithium manganate that 5g granular size concentrates on 0.3-10 micron again adds, and stirs shape Become suspension, then manganese acetate, Lithium hydrate, chromic nitrate, Lanthanum (III) nitrate are added, control lithium, The atomic ratio of lanthanum, chromium and manganese is 1.55: 0.15: 0.15: 0.85, and feed postition is by acetic acid After manganese, chromic nitrate, Lanthanum (III) nitrate are pre-mixed uniformly, add stirring 30min, by hydroxide Lithium, with after 100g water dissolution, adds, and constant temperature stirs into suspension；
Above-mentioned suspension is heated to 80 DEG C of evacuation process so that phenolic resin is by deposit Uniformly bonding is coated on spinel lithium manganate particle surface, and the process time is for until solvent is evaporated Entirely, presoma is obtained；
Above-mentioned presoma is placed in microwave oven, with nitrogen for protective gas heat treated, Nitrogen line flow velocity in microwave oven is not less than 5cm/min, and uses microwave hyperthermic treatment, rises Temperature speed is 200 DEG C/min, is heated to 1200 DEG C, isothermal reaction 0.5h, and protects at nitrogen Under be cooled to room temperature after, be ground into 6-15 micron, it is thus achieved that manganio composite positive pole.
Above-mentioned manganio composite positive pole is mixed with conductive agent white carbon black, adhesive PVDF, ratio For manganio composite positive pole: white carbon black: PTFE=80: 15: 7, grind with N-Methyl pyrrolidone Size mixing and be coated on 20 microns of thick aluminium foils, being prepared as test electrode.Above-mentioned electrode is cut out It is cut into the circle sheet of diameter 14mm, after suppressing with 0.5MPa pressure, just can be used as lithium ion battery Pole is tested.Using this electrode as positive pole, lithium sheet as negative pole, PC/DME/LiPF6As 2032 type button cells made by electrolyte, constant current 10mA/g charge and discharge electrical measurement between 2.5-4.2V Examination, specific discharge capacity is more than 260mAh/g.
Embodiment 5
Under room temperature, 0.85g phenolic resin is dissolved into molten by the ethanol using 275g concentration to be 95% Liquid；The spinel lithium manganate that 5g granular size concentrates on 0.3-10 micron again adds, and stirs shape Become suspension, then manganese acetate, Lithium hydrate, chromic nitrate, Lanthanum (III) nitrate are added, control lithium, The atomic ratio of lanthanum, chromium and manganese is 1.55: 0.15: 0.15: 0.85, and feed postition is by acetic acid After manganese, chromic nitrate, Lanthanum (III) nitrate are pre-mixed uniformly, add stirring 30min, by hydroxide Lithium, with after 100g water dissolution, adds, and constant temperature stirs into suspension；Weigh ANN aluminium nitrate nonahydrate 1.57g, adds with after 50g deionized water dissolving；
Above-mentioned suspension is heated to 80 DEG C of evacuation process so that phenolic resin is by deposit Uniformly bonding is coated on spinel lithium manganate particle surface, and the process time is for until solvent is evaporated Entirely, presoma is obtained；
Above-mentioned presoma is placed in microwave oven, with nitrogen for protective gas heat treated, Nitrogen line flow velocity in microwave oven is not less than 5cm/min, and uses microwave hyperthermic treatment, rises Temperature speed is 200 DEG C/min, is heated to 1200 DEG C, isothermal reaction 0.5h, and protects at nitrogen Under be cooled to room temperature after, be ground into 6-15 micron, it is thus achieved that manganio composite positive pole.
Above-mentioned manganio composite positive pole is mixed with conductive agent white carbon black, adhesive PVDF, ratio For manganio composite positive pole: white carbon black: PTFE=80: 15: 7, grind with N-Methyl pyrrolidone Size mixing and be coated on 20 microns of thick aluminium foils, being prepared as test electrode.Above-mentioned electrode is cut out It is cut into the circle sheet of diameter 14mm, after suppressing with 0.5MPa pressure, just can be used as lithium ion battery Pole is tested.Using this electrode as positive pole, lithium sheet as negative pole, PC/DME/LiPF6As 2032 type button cells made by electrolyte, constant current 10mA/g charge and discharge electrical measurement between 2.5-4.2V Examination, specific discharge capacity is more than 250mAh/g.
Embodiment 6
A kind of manganio composite positive pole, its be manganese source, lithium source, chromium source, lanthanum source, binding agent, Solvent composition covering be coated on outside spinel lithium manganate granule, wherein manganese source, lithium source, chromium source, The proportioning in lanthanum source is so that in covering, the atomic ratio of lithium, lanthanum, chromium and manganese is 1.73: 0.07: 0.11∶0.91；Wherein the consumption of binding agent is manganese source, lithium source, chromium source, the total consumption in lanthanum source Mass percent is calculated as 9%, and the consumption of solvent is manganese source, lithium source, chromium source, the total consumption in lanthanum source Quality is calculated as 20 times.
Described manganese source be manganese monoxide, manganese sesquioxide managnic oxide, mangano-manganic oxide, manganese dioxide, Hydroxyl oxidize manganese, manganese nitrate, manganese oxalate, manganese carbonate, formic acid manganese, any quality of manganese acetate Mixing.
Described lithium source is any mass mixing of lithium nitrate, lithium oxalate, lithium carbonate, lithium formate.
Described chromium source is any mass mixing of chromium oxide, chromic nitrate, chromium+oxalic acid, chromium carbonate.
Described lanthanum source be lanthana, Lanthanum (III) nitrate, lanthanum oxalate, lanthanum carbonate, formic acid lanthanum any Mass mixing.
Described binding agent be polyacrylonitrile, phenolic resin, epoxy resin, polyvinyl resin, Any mass mixing of furfural resin.
Described solvent is any mass mixing of water, ethanol, propanol.
Preparation method, puts into binding agent in solvent, is dissolved into solution, then is added thereto to point Spar lithium manganate particle, stirs into suspension, and adds manganese source, lithium source, chromium source, lanthanum source, In adition process, control temperature at 80 DEG C, to be added complete after, adjust temperature be 150 DEG C, Solvent is steamed completely, is passed through protective gas and is warmed up to 900 DEG C, isothermal reaction 33h, cooling, It is ground into 6-15 micron, it is thus achieved that manganio composite positive pole.
In above-mentioned temperature-rise period, its programming rate is 100 DEG C/min.Above-mentioned spinel manganese The input amount of acid lithium granule, accounts for 0.015 times of solvent by quality ratio.Above-mentioned spinel manganese Acid lithium granular size is 0.3-10 micron.Above-mentioned protective gas be helium, carbon dioxide, Any mass mixing in hydrogen.
Embodiment 7
A kind of manganio composite positive pole, its be manganese source, lithium source, chromium source, lanthanum source, binding agent, Solvent composition covering be coated on outside spinel lithium manganate granule, wherein manganese source, lithium source, chromium source, The proportioning in lanthanum source is so that in covering, the atomic ratio of lithium, lanthanum, chromium and manganese is 1.87: 0.08: 0.09∶0.99；Wherein the consumption of binding agent is manganese source, lithium source, chromium source, the total consumption in lanthanum source Mass percent is calculated as 10%, and the consumption of solvent is manganese source, lithium source, chromium source, the total consumption in lanthanum source Quality be calculated as 50 times.
Described manganese source be manganese monoxide, manganese sesquioxide managnic oxide, mangano-manganic oxide, manganese dioxide, Hydroxyl oxidize manganese, manganese nitrate, any mass mixing of manganese oxalate.
Described lithium source is any mass mixing of lithium nitrate, lithium oxalate.
Described chromium source is any mass mixing of chromium oxide, chromic nitrate, chromium+oxalic acid.
Described lanthanum source is any mass mixing of lanthana, Lanthanum (III) nitrate, lanthanum oxalate, lanthanum carbonate.
Described binding agent be polyacrylonitrile, phenolic resin, epoxy resin, polyvinyl resin, Furfural resin, polyacrylic resin, polyurethane resin, polyvinyl alcohol at least one.
Described solvent is any mass mixing of water, ethanol, propanol, ethylene glycol.
Preparation method, puts into binding agent in solvent, is dissolved into solution, then is added thereto to point Spar lithium manganate particle, stirs into suspension, and adds manganese source, lithium source, chromium source, lanthanum source, In adition process, control temperature at 120 DEG C, to be added complete after, adjust temperature be 200 DEG C, Solvent is steamed completely, is passed through protective gas and is warmed up to 1200 DEG C, isothermal reaction 48h is cold But 6-15 micron, it is ground into, it is thus achieved that manganio composite positive pole.
In above-mentioned temperature-rise period, its programming rate is 200 DEG C/min.Above-mentioned spinel manganese The input amount of acid lithium granule, accounts for 0.019 times of solvent by quality ratio.Above-mentioned spinel manganese Acid lithium granular size is 0.3-10 micron.Above-mentioned protective gas is argon, helium, dioxy Change any mass mixing of carbon.
Embodiment 8
A kind of manganio composite positive pole, its be manganese source, lithium source, chromium source, lanthanum source, binding agent, Solvent composition covering be coated on outside spinel lithium manganate granule, wherein manganese source, lithium source, chromium source, The proportioning in lanthanum source is so that in covering, the atomic ratio of lithium, lanthanum, chromium and manganese is 1.91: 0.03: 0.03∶0.97；Wherein the consumption of binding agent is manganese source, lithium source, chromium source, the total consumption in lanthanum source Mass percent is calculated as 1%, and the consumption of solvent is manganese source, lithium source, chromium source, the total consumption in lanthanum source Quality is calculated as 5 times.
Described manganese source be manganese monoxide, manganese sesquioxide managnic oxide, mangano-manganic oxide, manganese dioxide, Hydroxyl oxidize manganese, manganese nitrate, manganese oxalate, manganese carbonate, formic acid manganese, manganese acetate, high manganese lithium, LiMn2O4, any mass mixing of spinel lithium manganate.
Described lithium source is lithium nitrate, lithium oxalate, lithium carbonate, lithium formate, Quilonorm (SKB), hydrogen-oxygen Change any mass mixing of lithium.
Described chromium source is chromium oxide, chromic nitrate, chromium+oxalic acid, chromium carbonate, chromic formate, acetic acid Any mass mixing of chromium.
Described lanthanum source is lanthana, Lanthanum (III) nitrate, lanthanum oxalate, lanthanum carbonate, formic acid lanthanum, acetic acid Any mass mixing of lanthanum.
Described binding agent be polyacrylonitrile, phenolic resin, epoxy resin, polyvinyl resin, Furfural resin, polyacrylic resin, polyurethane resin, any mass mixing of polyvinyl alcohol.
Described solvent be water, ethanol, propanol, ethylene glycol, glycerol, benzene, toluene, third Ketone, butanone, butanone, chloromethanes, benzoyl, formic acid, DMF, N- Any mass mixing of methyl pyrrolidone.
Preparation method, puts into binding agent in solvent, is dissolved into solution, then is added thereto to point Spar lithium manganate particle, stirs into suspension, and adds manganese source, lithium source, chromium source, lanthanum source, In adition process, control temperature at 5 DEG C, to be added complete after, adjust temperature be 60 DEG C, Solvent is steamed completely, is passed through protective gas and is warmed up to 600 DEG C, isothermal reaction 0.5h is cold But 6-15 micron, it is ground into, it is thus achieved that manganio composite positive pole.
In above-mentioned temperature-rise period, its programming rate is 0.1 DEG C/min.Above-mentioned spinel manganese The input amount of acid lithium granule, accounts for 0.01 times of solvent by quality ratio.Above-mentioned spinelle mangaic acid Lithium granular size is 0.3-10 micron.Above-mentioned protective gas be air, oxygen, nitrogen, Any mass mixing in argon, helium, carbon dioxide, hydrogen.
Embodiment 9
On the basis of the above embodiments 6, other are all with embodiment 6, in order to make manganese The structure of base composite positive pole is the most stable, improves this positive electrode as lithium battery anode The performance of battery prepared by material, such as specific capacity, service life etc.；It is in preparation process, After binding agent is dissolved into solution, before adding spinel lithium manganate granule, also include Add the step of magnesium salt.Wherein addition accounts for the 0.1% of lithium source quality respectively.At above-mentioned addition aluminum The amount of salt can not be too much, otherwise will affect the specific capacity of composite positive pole.
Embodiment 10
On the basis of the above embodiments 6, other are all with embodiment 6, in order to make manganese The structure of base composite positive pole is the most stable, improves this positive electrode as lithium battery anode The performance of battery prepared by material, such as specific capacity, service life etc.；It is in preparation process, After binding agent is dissolved into solution, before adding spinel lithium manganate granule, also include Add aluminium salt, zinc salt and the step of magnesium salt.Wherein addition accounts for the 4% of lithium source quality respectively.? The amount of above-mentioned addition aluminium salt, zinc salt and magnesium salt can not be too much, otherwise will affect anode composite material The specific capacity of material.
Embodiment 11
On the basis of the above embodiments 6, other are all with embodiment 6, in order to make manganio multiple The structure closing positive electrode is the most stable, improves this positive electrode as anode material of lithium battery The performance of the battery of preparation, such as specific capacity, service life etc.；It is in preparation process, is inciting somebody to action After binding agent is dissolved into solution, before adding spinel lithium manganate granule, also include adding Aluminium salt, the step of zinc salt.Wherein addition accounts for the 5% of lithium source quality respectively.At above-mentioned addition aluminum Salt, zinc salt amount can not be too much, otherwise will affect the specific capacity of composite positive pole.

Claims (10)

1. a manganio composite positive pole, it is characterised in that it is manganese source, lithium source, chromium Source, lanthanum source, binding agent, solvent composition covering are coated on outside spinel lithium manganate granule, its Middle manganese source, lithium source, chromium source, the proportioning in lanthanum source are so that lithium, lanthanum, chromium and manganese in covering Atomic ratio is 1.91-1.55: 0.03-0.15: 0.03-0.15: 0.97-0.85；Wherein bond The consumption of agent is that manganese source, lithium source, chromium source, the mass percent of the total consumption in lanthanum source are calculated as 1-10%, The consumption of solvent is that manganese source, lithium source, chromium source, the quality of the total consumption in lanthanum source are calculated as 5-50 times.
2. manganio composite positive pole as claimed in claim 1, it is characterised in that described Manganese source be manganese monoxide, manganese sesquioxide managnic oxide, mangano-manganic oxide, manganese dioxide, hydroxyl oxidize manganese, Manganese nitrate, manganese oxalate, manganese carbonate, formic acid manganese, manganese acetate, high manganese lithium, LiMn2O4, point At least one of spar LiMn2O4.
3. manganio composite positive pole as claimed in claim 1, it is characterised in that described Lithium source be lithium nitrate, lithium oxalate, lithium carbonate, lithium formate, Quilonorm (SKB), Lithium hydrate at least A kind of.
4. manganio composite positive pole as claimed in claim 1, it is characterised in that described Chromium source be chromium oxide, chromic nitrate, chromium+oxalic acid, chromium carbonate, chromic formate, at least the one of chromium acetate Kind.
5. manganio composite positive pole as claimed in claim 1, it is characterised in that described Lanthanum source be lanthana, Lanthanum (III) nitrate, lanthanum oxalate, lanthanum carbonate, formic acid lanthanum, at least the one of lanthanum acetate Kind.
6. manganio composite positive pole as claimed in claim 1, it is characterised in that described Binding agent be polyacrylonitrile, phenolic resin, epoxy resin, polyvinyl resin, furfural resin, Polyacrylic resin, polyurethane resin, polyvinyl alcohol at least one.
7. manganio composite positive pole as claimed in claim 1, it is characterised in that described Solvent be water, ethanol, propanol, ethylene glycol, glycerol, benzene, toluene, acetone, butanone, Butanone, chloromethanes, benzoyl, formic acid, DMF, N-Methyl pyrrolidone At least one.
8. manganio composite positive pole as claimed in claim 1, it is characterised in that described Covering, its raw material also includes aluminium salt, zinc salt or magnesium salt, and wherein addition accounts for lithium source matter respectively The 0-5% of amount.
9. the preparation method of the manganio composite positive pole as described in any one of claim 1-8, It is characterized in that, binding agent is put in solvent, be dissolved into solution, then it is brilliant to be added thereto to point Stone lithium manganate particle, stirs into suspension, and adds manganese source, lithium source, chromium source, lanthanum source, In adition process, control temperature at 0-120 DEG C, to be added complete after, adjust temperature be 60-200 DEG C, solvent is steamed completely, be passed through protective gas and be warmed up to 600-1200 DEG C, permanent Temperature reaction 0.5-48h, cools down, is ground into 6-15 micron, it is thus achieved that manganio composite positive pole.
10. the preparation method of manganio composite positive pole as claimed in claim 8, its feature Being, it is after being dissolved into solution by binding agent, before adding spinel lithium manganate granule, Also include adding aluminium salt, zinc salt or the step of magnesium salt.
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